Manufacture of methylcyclohexenes



Nov. 4, 19.47.

A. G. OBLAD ETAL.

MANUFACTURE OF METHYLCYCLOHEXENES Filed April l5, 1946 A/ex 6j Ob/ao Evere/ 6er/f7 IN V EN TORS BY Cb. @7L

. ATTORNEY prene,

Patented Nov. 4, y 1947 i 2,430,131 UNITED STATES `PATElSiT ori-lcs MANUFACTURE or METHYLoYcLonExENEs Alex G. Oblad and Everett Gorin, Dallas, Tex., assignors, by mesne assignments, to Socony-Vacuum Oil Company, Incorporated, New York,

N. Y., a corporation of New York Application April 15, 1946, Serial No. 662,155

6 Claims. (Cl. 26o-666) This invention relates to the conversion of aliphatic hexenes to methylcyclohexenes. More particularly, this invention relates to a process for the pyrolysis of propylenedimer polymers to form a mixture containing equimolar amounts of ethylene and isoprene and/or equimolar amounts of propylene and 1,3-butadiene, hereinafter sometimes referred to as butadiene, and the condensation of either or both of these olefln-diolefin pairs to form lmethylcyclohexene1 and/or 4-methylcyclohexene-l.

Heretofore it has been necessary t utilize elab- 'orate fractionating equipment tofsegregate 1,3-

butadiene'and isoprene from associated hydrocarbons by absorptive fractionation in order to. obtain these dienes in suiiiciently high concentration t0 condense them with mono-olens in .the

Diels-Alder type reaction. Thus, an aqueous solution of cuprous ammonium acetate has been used to obtain relatively pure 1,3-butadiene from a mixture containing other C4 hydrocarbons. It

is highly desirable to obtain isoprene and 1,3-butadiene free of'associated-hydrocarbons which interfere in the condensation reactionV with Specic oleiins, by simple distillative-fractionation, in order to be able to carry on the condensation reaction and the cooperating production of olein and dioleiin intermediates on a continuous basis.

It is known in the art to pyrolyze propylene polymers to produce dienes.l For example, U. S.

Patent 2,339,560, issued to Martin DeSmo et al.,

ture consisting substantially of 1,3-butadiene, isoprene, ethylene, and propylene in stoichiometr'ic proportions suitable for the .production therefrom of 4-methylcyclohexene-1 and l-methylcyclohexene-1. Other objects of the invention will appear hereinafter.

e We have found that isoprene and 1,3-butadiene of suitable purity for condensation with ethylene and propylene can be produced by pyrolizing al selected cut of propylene polymer.' In our process, We pyrolyze that part of the propylene polymer which yields a product the C5 fraction of which contains a relatively high per cent of iso- The C4 fraction of the product contains a relatively high per cent of 1,3-butadiene associatedy with a. minor amount of isobutylene which does not react with the butadiene and hence does not interfere with the condensation of the butadiene with propylene. We exclude from the Qyrolysis step those components of the propylene polymer which yield other dienes. The stoichiometric quantities of ethylene and isoprene components of the pyrolyzed product are condensed to form l-methylcyclohexene-l and the substantially equal molecular quantities of propylene and 1,3-butadiene components are condensed to form 4-methylcyclohexene-l in separate cooperating Diels-Alder type condensation steps of the process.

Propylene dimers may be divided into two groups of compounds. The rst group consists predominantly of 2methylpentene2, 'with smaller amounts of 2-methylpentene-l and S-inethylpentene-2, and constitutes the 60 C.to70 C. fraction of the dimer. The second group comprising the remainder of the dimers contains such compounds as S-methylpentene-l, ii-methylpentene-l, and smaller amounts of other hexenes. We have found that the pyrolysis of the first group of compounds results predominantly in the production of isoprene inthe C5 fraction and predominantly 1,3-butadiene in the C4 fraction ofthe cracked dimers. The pyrolysis of the remaining components of the dimer results largely in the production of light olefins and only a relatively small amount of isoprene and butadiene. The pyrolysis of the iirst group of compounds results in the production of ethylene and propylene in molecular proportions substantially equivalent to the isoprene and 1,3-butadiene re.- spectively in the product.

As indicated above, feed to our process consists of that fraction of propylene dimer which is predominantly 2-methylpentene-2 Valthough smaller amounts of 3-methylpentene-2 and 2-methylpentene-l are also present. The polymerization of propylene to produce a dimer consisting in large part oi these components may be carried out over catalysts of the alumina-silica type or "in the presence of a dilute aqueous solution of phosphoric acid. The liquid product from the polymerization step is fractionated and fraction boiling between60 C. and '10 C. is pyrolyzed at a temperature within the range of from about '750 C. to about 850 C., preferably Within the range of from about '775 C. to 825 C. at a contact time within the range of from y0.005 second to about 2.0-seconds. Contact time is determined by dividing the volume of the reaction space by the volume of reactants charged per second measured as a gas under standard conditions of temperature and pressure. The pyrolysis reaction is preferably carried out at partial pressures of the dimer below atmospheric pressures, that is, down to a. pressure of 0.1 atmosphere partial pressure of the dimer feed. The total pressure in the pyrolysls zone should be within the range of from about 1 atmosphere to about 3 atmospheres gage. A diluent such as steam is incorporated with the feed to' reduce the partial pressure of the polymer to the desired level.

The product from the pyrolysis zone is rapidly quenched to temperatures below 300 C. The

product is fractionated to obtain separate streams containing ethylene, propylene, 1,'3-butadiene, and iscprene. The ethylene and isoprene streams are passed to a condensation zone which mayY consist of any suitable type reactor or which may consist of a multiplicity of reactors in series wherein l-methylcyclohexene-l is produced. The streams of propylene and butadiene are passed to a similar but separate condensation zone wherein 4-methylcyclohexene-1 is produced. The condensation reactors are maintained at temperatures within the range of from about 300 C. to about 375 C., preferably from about 315 C. to 350 C. An internal ratio of mono-olefin to diene of at least 5 to 1 to 30 to 1 or higher is maintained in the condensation reactor.

The total residence time of the mono-olefindiene mixture in the condensation reaction zone, that is, the contact time of isoprene with ethylene and the contact time of 1,3-butadiene with propylene, .is a function of the temperature and the pressure; that is, the residence time should be shorter the higher the temperatureand pressure.

.When operating the condensation reactors at temperatures cf from about 350 to about 375 C.,

pressures of from about 70 to 150 atmospheres are suitable and the residence time'of the mono-oleiin-diene mixture in the series of reactors will be within the range of from about 6 minutes to about 20 minutes. On the other hand, when temperatures within the range of from'about 300 C. to 325 C. are maintained in the condensation zone, higher pressures within the range of from about 175 to about 275 atmospheres are suitable. Residence times when operating in the lower temperatures range will be within the range of from about 1/2 hour to 5 hours. When operatingthe condensation process at intermediate temperatures, pressures and residence times between these extremes should be used. In general, the condensation of propylene with 1,3-butadene requires somewhat longer residence time to obtain substantially complete condensation of the dimer with the mono-olefin in a single pass through the series of reactors. t

The products from the respective condensation zones are passed to fractionators for separation of the methylcyclohexenes from diene polymers, ethylene, and propylene, and unreacted components of the C4 and C5 fractions. Usually the products from the condensation zones contain 'little or no unreacted dienes. The product from the butadiene-propylene condensation reactors contains some isobutylene. For the better understanding of our invention reference may be made to the drawing which forms a part of this specification and represents diagrammatically one form of apparatus suitable for effecting the process o the invention.

Turning now'to a detailed consideration of the drawing, the liquid charge which consists of the 60 C.to70 C. fraction of propylene dimer is introduced to the process by means of pump I I in line I2. The 60 C.-to-70 C. fraction is passed through line I3 to coil I4 in furnace I5. An inert diluent such as water or steam is introduced to line I3 from line 20. The amount of'diluent added to line I3 should be suicient to maintain the partial pressure of propylene dimer in coil I4 below atmospheric pressure. The temperature of the stream of vaporized dimer in coil I4 preferably should be maintained within the range of from about 775 C. to about 825 C. The mixture of dimer and steam is fed to coil I4 at a rate to give a contact time within the limits of 0.005 and 2.0

' seconds, preferably within the range of from about 0.05 to about 0.5 second. The vproduct passes from coil I4 to line 2I and is quenched to a temperature below 300 C. with water introduced to line 2'I through line 22. The quenched pyrolyzed product passes' through line 23 to condenser 24 where the majonporion of the water is separated from the hydrocarbon product and the mixture is passed by means of pump 25 in line 26 to. separator 21.

Separator 21 is maintained at a temperature within the range of from about 50 C. to about '75 C. and at a pressure up to 2 atmospheres, preferably about atmospheric. Water which is condensed from the pyrolyzed product is withdrawn from separator 21 through line 28 which leads to line 29. If desired, the liquid condensate from separator 21 may be sent to a tar separator (not shown) for the separation of higher boiling material produced in pyrolysis coil I4. A part of this water is passed by means of pump 30 through line 3| to cooler 32 and thence by line 22 to line 2| to' be reused as quench water. The remainder of the water in line 29 is passed through line 33 to heater 34 and thence by line 35 to line 20 which joins line I3. This water may be introduced to line I3 in the form of water or steam to act as a diluent of the hydrocarbon passing to coil I4.

- The gaseous products separatedin separator 21 pass overhead through line 40 and are pressured by means of compressor 4I to about 200 pounds per square inch. The product passes through line 42 to cooler 4'3 and thence through line 44 to separator 45 where additional water, undecomposed hexenes, and a part of the C5 fraction of the pyrolyzed mixture are separated as condensate from the lighter product. The hydrocarbon condensate forms as a liquid layer superimposed on the water condensate in separator 45. Water is recycled from the bottom of separater 45 through lines 46, 41, and 29. Noncondensed gaseous product passes from separator l45 through line 48 to drier 49' where the last'traces of water vapor are removed from the product. Substantially Water-free product vapors from drier 49 are picked up by means of compressor 50 in line 5I, which leads to partial condenser 52 where'` the major portion of the hydrocarbon vapors is condensed. The .mixture of vapors in the hydrocarbon condensate passes from condenser 52 through line 53 to fractionator 54. Imiquid hydrocarbon condensate in separator 45 is passed by means of pump 55 in line 56 to line 53 and is thus made a part of the feed stream passing to fractionator 54. 4 l

Fractionator 54 serves to separate the Ca hydrocarbons and lower boiling hydrocarbons from the C4 hydrocarbons and higher boiling hydrocarbons. Fractionator 54 is operated at a pres- `sure Within the range of from about 400 to 450 pounds per square inch. Ca and lower boiling hydrocarbons pass overhead from fractionator 54 through line 51 to condenser 58 and thence through line 59 to reiiux accumulator 60. The overhead product from fractionator 54' consists of about 2 moles of propylene and C2 hydrocarbons, a major portion of whichlCz hydrocarbons is ethylene, for each 3 moles of methane and hydrogen. A major proportion of the lighter product is methane. Liquid condensate in accumulator 60, which contains propylene and a part of the ethylene, is withdrawn through line 6I by means of pump 62. A part of this condensate is passed through line 63 to be used as reflux in fractionator 54, and the remainder is passed through line 64;to fractionator 65. The C4 and higher boiling hydrocarbonsv are withdrawn from the bottom of fractionator '54 through line 68. Propylene is separated from the C2 hydrocarbon in fractlonator 65, which is operated at a pressure within the lrange of from about 450 to 500 pounds per square inch. The C2 hydrocarbons consisting of at least 80 per cent ethylene and a part of the methane of the pyrolyzed product pass` overhead from fractionator 65.through line 10 to condenser 1I and thence through line 12 to reflux accumulator 13. At least a part of the condensate which consists primarily of ethylene is passed from accumulator 13 by means of pump 14 in line 15 through line 16 to be used as reflux in fractionator 65. The remainder of the liquid condensate from accumulator 13 may be vaporized in condensers 58 and/or 1| inl order to provide cooling means for the condensation ofv the light gases from the fractionators 54` and/or 65, and the vaporized condensate is then passed through lines 11 Yand 18 'to ethylene recovery tower 80.= The gaseous streams from the accumulators 60 and 13 which comprise methane, hydrogen, ard a, part of the ethylene pass overhead through lines 8| and 82 which lead to line 18 by way of lire 83. Thus, we recover in tower 80 any ethylene which is not condensed in the accumulators. If desired, a part of the ethylene stream in line 11 may be sent directly through line 84 to line |00 through which substantially pure ethylene is passed to the ethylene-isoprene condensation step of the process. Liquid propylene is withdrawn from the bottom of tower 65 through line 85 and is passed to the propylenebutadiene condensation step described hereinbelow.

The stream of light hydrocarbon gases and hydrogen in line 18 will contain from about25 6 lease valve 92 and passes thence tol desorption tower 93. The ethylene is desorbed from the solution by reduction of pressure on the solution and/or by the application of heat to the solution by means of steam coil 94 in the bottom of tower 93. Desorbed cuprous chloride solution is recycled from the bottom of tower 93 through line 95, which leads to lline 81. 96 is installed in line 95 in order to maintain the temperature of the solution within the range of 5 C. to 35 C. A relatively pure ethylene stream passes overhead from tower 93 through line 91, which joins line |00 leading to the ethylene-isoprene condensation step of our process. If desired, a part of the relatively pure ethylene stream may be diverted through line 98 by means of compressor 99 and introduced near the bottom of tower 80. The introduction of pure ethylene to tower 80 below the point of introduction of the impure ethylene stream serves to strip the solution of any absorbedA propylene and substitute therefor absorbed ethylene. l

`Returning now to the description of the fractionation of the. C4-lof hydrocarbons recovered from tower 54, the stream of hydrocarbons in line 66 is passed to fractionator IOI which is operated at a pressure of from about 5 atmospheres `to about 10 atmospheres gage. The Ce and higher mole per cent to about or 55 mole per cent of ethylene. In tower 80 which may suitably be packed with inert packing material, the stream of gas from line 18 is contacted at a temperature of from about 5 to 35 C. with an aqueous solution containing cuprous chloride introduced to tower 80 by means of pump 86 in line 81. Contact of the gas with this solution is made at pressures within the range of from about 3 atmospheres to about 30 atmospheres. The use of an aqueous solution of cuprous chloride for absorbing ethylene from a gas stream is described'by Gilliland and Seebold in Industrial and Engineering Chemistry, vol. 33, September, 19.41, pages 1143- 1147.' The solution should contain about 3 gram4 boiling fraction consisting substantially of undecomposed propylene-dimer, that is, usually at least 50 mole per cent of undecomposed dimer, is withdrawn from tower |0| through bottom drawoff line |02. A part of this fraction may be removed from the process through line |03; however, we prefer to recycle this fraction through lines |04 and |05 to line\|2. A C5 fraction containing at least 90 mole per cent of isoprene4 is withdrawn as a side stream from fractionator IGI through line |06 by means of pump. |01. The major part of this isoprene stream is passed through line |08 to the ethylene-isoprene condensation zone described hereinbelow.

Y The overhead product from tower |0| which consists of C4 hydrocarbons comprising a major proportion of LIS-butadiene and a minor proportion of isobutylene passes through line '|09 to condenser ||0 and thence through line to reux accumulator ||2. The liquid condensate from accumulator ||2 is removed therefrom by means of pump 3 in line ||4. A part of this liquid stream is diverted through line I|5 to be used as reux in tower |04. The remainder of this liquid stream is passed through line |I6 which connects with manifold feed line l |1. Manifold line II1 supplies butadiene to the propylene-butadiene condensation reactors described hereinafter. If desired, an inhibitor such as aniline may be added to the butadiene stream in line ||6 and to the isoprene stream in line |08 by lines not shown in the drawing in order to inhibit the oxidation and/or polymerization of the dienes.

The condensation apparatus wherein ethylene and isoprene are condensed to form l-methyl- The compressed gas is passed through heater |21 V where it is heated preferably to a temperature,

' within the range of from about 315 C. to 350 C. The heated gas passes through lines |28 and Solution cooler A 7 |29 to reactor |2|.` The ethylene is circulated throughthc reactor system inorder to introduce a -high concentration of ethylene therein bfore introduction of the isoprene. The gas passes from reactor |2| through line |30 to reactor |22 and Vthence through line |3| to reactor |23. From reactor |23 the ethylene stream passes throughline |32, valved line |34, and 1ine |35 to line |26, valves |36 and |31 in lines |38 and |35 respectively being closed; When the reactor system has been heated and pressured, valve |39 in line |34 is closed and valves |36 Vand |31 are placed in' the open position. Valve |40 in line |08 is then opened and isoprene is passed to `heater |4| wherein the temperature `of the isoprene is raised to about 100 C. and the stream of warm isoprene passes through line |42 and valve |43 to line |29 where it is injected into the stream of hot ethylene gas, passing to reactor We maintain an ethylene-to-isoprene ratio of A at least 5 to 1 in reactors |2|, |22, and |23. The

as a continuous stream to reactor |22 to whichA additional isoprene is added from line |44 which leads -from line |42 and connects with line |30. The average residence time of the reaction mixture in reactor |22, which is maintained at approximately the same temperature and pressure as reactor |2|, is Within the range of from about 15 minutes to about 60 minutes. The reaction mixture passes through line |3| to reactor |23 which is maintained at about the same temperature and pressure as reactors |2| and |22. The

. average residence time of the reaction mixture in reactor |23 is within the range of from about 10 minutes to about 40 minutes or for a suiicient time t'o complete substantially the reaction of isoprene lin themixture.` The last reactor of the series of reactors serves .as a reaction kzone in which residual isoprene is reacted and hence additional isoprene is not added to the product stream inline |3I.

The reaction mixture passes from reactor |23 closed and valve |83 in line |84 open, the hot from line |05 to line |2 and thence through line I3 to pyrolysis coil |4 in furnace I5 wherein it is cracked to produce isoprene. Relatively pure 1- methylcyclohexene-l product is withdrawn from fractionator through line |53. A relatively small Cs stream consisting substantially of pentenes and pentanes is also Withdrawn from frac- 4tionator |50 trap-out linev |54. If desired, this stream which may containa small amount of isoprene may be recycled to coil |4 through lines |55, |04, |05 and |3.

Turning now to the step of the process wherein propylene is condensedwth butadiene, the condensation reactors are represented by chambers |B|, |62, and |63. These reactors are operated under the same conditions of temperature, pressure, and residence times as reactors |2 |22, and |23. Propylene from line 85 is passed by means of pump |10 in line |1| ,through line |12 to heater |13 Where the propylene is raised in vtemperature to at least' 300 C. The propylene vapor at a pressure of about 100 atmospheres passes through line |14 to reactor |0|. The heated vapor is circulated through the.series of reactors in order to make provision for a. relatively high ratio of propylene to ybutadiene in the reactor system. The mole ratio of propylene to butadiene in reactor |6| should be at least 5 to 1 and the ratio may be as high as 30 to 1 or higher in reactors |6|, |62, and |63. The hot propylene gas passes from reactor |6| througlrlines |16 and |11 to reactor |62 and thence through line |18 to reactor |63. With valve |8| in line |82 propylene gas is circulated from reactor |63 through lines |80, |84, |86, |81, and |14, and heater |88 by means of blower |80.

Valve |8| in line |32 is now placed in the open position, valve |83 in line |84 is closed, and liquid 1,3-butadiene from line ||6 isintroduced to the propylene stream through lines |1, |11, and |90. The ratio of propylene to LIS-butadiene tends to increase as the mixture of gases passes through the series of reactors and hence 1,3-butadiene through lines |32 and |38 to partial condenser |46 wherein C5 hydrocarbons, 1methylcyclohex ene-1, and isoprene polymer are condensed from the gaseous mixture. Since the isoprene is substantially completely condensed 'to the methylcyclohexene or to isoprene polymer, the amount of C5 hydrocarbons in the product is relatively small. The mixture of ethylene gas and liquid product passes through linev |41'to gas separator |48. Ethylene is recycled from separator |48 through line |35 to line |28. Liquid condensate from separator |48 passes through line |49 to fractionator |50.

Fractionator |50 is operated at from about 5 to about 10 atmospheres for the separation of the liquid product from residual ethylene which passes overhead through .lines |5| and |35 to line |26. The dimer of isoprene is withdrawn connects with recycle line |05. The dimer passes .is introduced to each of the two reactors in order to maintain a sufciently high ratio of butadiene to propylene to obtain reasonably high reaction rates. On the other hand, the ratio of propylene to 1,3-butadiene should be relatively high in order to prevent the formation of butadiene dimer.

The reaction mixture passes in series through reactors |6| and |02 wherein a major proportion of the butadiene reacts with a part of the propylene to form 4-methylcyclohexene-1. A part of the butadiene is converted to butadiene dimer. The mixture then passes through line |18 to reactor |63. Reactor |63 serves as a ycleanup reaction zone wherein any residual butadiene in the reaction mixture is converted to 4-methy1- cyclohexene-l. Hence, additional butadiene is not added to this reactor which represents the last reactor of the series of reaction zones.

Thereaction product consisting substantially of propylene,'4-methylcyclohexene-1, butadiene dimer, and isobutylene passes from reactor |63 through lines and 82 to partial condenser |9| which is maintained at such a temperature that substantially all of the product except unreacted propylene is condensed. The condensed product passes from condenser |8| through line |92 to separator |93. Gaseous propylene is recycled through line |94 which connects with liney |85. LThe liquid product from separatory |93 passes through line |95 to fractionator |96.

Fractionator |96 is operated at a pressure from 9 about 150 to about 250 pounds per square inch. Butadiene dimer is withdrawn from the bottom of fractionator |98 through line |01 and is re-` cycled through lines |04, |05, I2, and I3 to coil I4 in furnace I5. Propylene is withdrawn as overhead through line |98 and passes to condenser |99 and thence through line 200 to reiiux accumulator 20|. Condensate in the vaccumulator 20| is passed in part by means of pump 202 in line 203 through line 204 to serve as reiiux in tower |96.. The remainder of vthe EXAMPLE 1 Propylene was dimerized by passing the olefin 'over alumina silica catalyst of the Gayer type at a temperature of 360 C. and at a l0-pound gage pressure. A space velocity of about 230 volumes (S. T. P.) of propylene per volume of catalyst space per hour was maintained to give a yield of 45.8 per cent of dimer based on the propylene converted. Approximately 42.8 per cent of the propylene feed was converted to polymer.

VThe dimer consisted mainly-of Z-methylpentenes of which 2-methylpentene-2 predominated. Boiling range of the dimerwas approximately 50 C. to 75 C. This material was fractionated to produce a 60to-70 C. fraction which represented approximately 80 per cent of the dimer and 36.7 per cent of the total polymer produced.

The above 60-to-70" C. fraction of the dimer was diluted to volume per cent with nitrogen and pyrolyzed at 800 C. under approximately atmospheric pressure and at a contact time of 0.05 second. Under these conditions, 71.3 per cent of the dimer was decomposed. The volume per cent of the various products in the effluent and their yields are given in the table below.

It is to be noted that theyield of isoprene per 100 moles of dimer decomposed was 46.7 moles.

The yield of ethylene with which We condense the isoprene to form 1-methylcyclohexene-1 was 41.1 moles per 100 moles dimer decomposed. The yields of 1,3-butadiene and propylene which we condense to form 4-methylcyclohexene-1 were 14.3 and 13.2 respectively.

Example 2 illustrates the step of the process wherein 1,3-butadiene is condensed with propylene.

EXAMPLE 2 A mixture containing propylene and butadiene in the ratio of about 5.6 moles of propylene to 1 mole of butadiene, and also a small amount of aniline inhibitor was heated in an autoclave at a temperature of about 300 C. for al period of 2 hours. The pressure at 300 C. operating temperature was about 143 atmospheres. The analysis of the product'indicated that 23.8 per cent of the butadiene charged was converted to 4-methylcyclohexene-l. The boiling point of 4-methylcyclohexene-l fraction was 102.5 C. The index of refraction, 11u25, of the methylcyclohexene product was 1.4390. The 1,3-butadiene dimer produced amounted to 63.6 per cent of the butadiene charged. The remainder of the butadiene,- that is, 12.6 per cent of the butadiene charged was converted to a higher boiling polymer.

Example 3 illustrates the step of the process wherein isoprene is condensed with ethylene to form l-methylcyclohexene-l.

EXAMPLE 3 A mixture consisting'of 88.9 mole per cent of ethylene and 11.1 mole per cent ofisoprene was heated at a temperature of about 320 C. in an autoclave at a pressure of about 132 atmospheres for a period of one hour. Upon analysis of the product it was found that 53.6% of the isoprene charged was converted to l-,methylcyclohexene-l having a boiling point of 111 C. (760 mm.) and an index of refraction (11u20) of 1.4500. The amount of unreacted isoprene amounted to 26.8% of the isoprene charged. About 20% of the isoprene was converted to isoprene polymer which substantially equimolecular amounts of isoprene and ethylene, and also substantially equimolecular amounts of L3-butadiene and propylene. These reactants are 'present in the pyrolyzed product stream in sufficient concentration to make possible their recovery and use in the condensation reactions to produce the methylcyclohexenes lwithout the expenditure of large sums of money for fractionating equipment. The isoprene is present to the extent of at least mol per cent in the C5 fraction of the pyrolyzed product. This makes possible the separation by distillative fractionation of isoprene of sufficient purity for condensation with ethylene. The 1.3- butadiene is present to the extent of at least 55 -or 60 per cent of the C4 fraction of the p vrolyzed product, the other component being isobutylene. Isobutylene does not condense with 1,3-butadiene in the Diels-Alder typey condensation and hence the presence of the isobutylene does not interfere with the reaction of 1,3-butadiene with proplyene in the formation yof 4-methylcyclohexene-1.

It will be understood that the flow diagram pre- 11 and that our invention is not to be restricted to the details shown. Thus, we may use a smaller number or greater number of reaction chambers a 12 1,3-butadiene, and isoprene, (3) Ycontinuously passing to a reaction zone the ethyleneand isoprene-containing streams of step 2 and formin the condensation step of our process. yOn the steps of (1) atalyticallypolymerizing proplyeneunder conditions of temperature and pressure to form predominantly propylene dimer, (2) fractionating the product of step 1 to obtain a fraction boiling within the range of from 60 C. to 70 C., (3) pyrolyzing the 60 C.to70 C. fraction of step 2 under conditions of temperature,A pressure, and contact time to obtain a product stream containing substantially equimolecular quantities of isoprene and ethylene and containing substantially equimolecul'ar quantities of LS-butadienev and propylene, (4) fractionating the product.

stream of step 3 to obtain separate hydrocarbon streams containing isoprene, 1,3-butadlene, ethylene. and propylene, thermally condensing the isoprene and ethylene of step 4 in a reaction zone to obtain a product stream containing 1-methylcyclohexene-l, (6) thermally condensing the 1,3- butadiene and propylene of step 4in a separate reaction zone to obtain a product stream containing 4-methylcyclohexene-1. and (7) fractionating the product streams of steps 5 and 6 to recover 1-methylcyclohexene-1 and 4-methylcyclohexene-l. l

2. The process for the manufacture of I-methylcyciohexene 1 and 4 methylcyclohexene l .which comprises the steps of (1) fractionating propylene polvmerlto obtain'a fraction boiling in ing therein a product stream containing' 1- methylcyclohxene-l, (4) continuously passing to a second reaction zone the propyleneand 1,3-

-butadiene-containing streamsof step 2 and forming therein a product stream containing 4- methylcyclohexene-l, (5) fractionating the product streams of steps 3 and 4 to obtain separate streams consisting substantially of ethylene,

propylene, 1methylcyclohexene1, 4-methylcyclohexene-l, and a polymer of 1,3-butadiene,

(6) recycling the vethylene stream of step 5 to step 3 and the propylene `stream of step 5 to step 4, (7) recycling the polymer of step 5 to step 1 of the process, and (8) continuously recovering l-methylcyclohexene-l and 4'methylcyclohexene-l from step 5 of the process.

4. The continuous process for the manufacture o f 1methylcyclohexene1 and 4-methylcyclohexene-l which comprises the steps of (l) fractionating a propylene dimer to obtain there- Afrom a fraction consisting of a mixture of the range of from 60 C. to 70 C., (2) pyrolyzing the 60 C.to70 C. fraction of step 1 under condii-ions o f temperature, pressure, and contact time to obtain a product stream containing substantially equimolecular quantities of isoprene and ethylene and containing substantially equimolecular quantities of 1,3-butadiene and lpropylene, (3) fractionating the product stream of step2 to obtain separate hydrocarbon streams containing isoprene. 1,3-butadiene, ethylene, and propylene. (4) continuously passing the isoprene and ethylene containing streams of step 3 through a series of reaction chambers to form a product stream containing l-methylcyclohexene-1, (5) continuously passing the streams containing propylene and 1,3-butadiene through a second series of reaction chambers to form a product stream containing 4-methylcyclohexene-1, and (6) recovering said l-methylcyclohexene-1 and 4-methylcycloheXene-1 from the product streams of steps 4 and 5 of the process.

3. The continuous process for the manufacture of 1-methylcyc1ohexene-1 and 4-methylcyclohexene-l which comprises (1) continuously pyrolyzing the 60 C.-to70 C. fraction of hexenes boiling in the range of from 60 C. to C., (2)'pyrolyzing the 60 C.'to70 C. fraction of step 1 in a heating' zone at a temperature within the range of from about 750 C. to about 850 C., (3) separating from the product of the heating zone of step 2 by distillative fractionation at least four fractions comprising a fraction containing hydrogen, methane, ethylene and ethane, a C3 hydrocarbon yfraction consisting substantially of propylene, a C4 hydrocarbon fraction containing a major proportion of 1,3- butadiene, and a C5 hydrocarbon fraction consisting substantially of isoprene, (4) separating ethylene from the ethylene-containing fraction of step 3, (5) continuously passing the ethylene from step 4 and the C5 hydrocarbon fraction of step 3 through a reaction zone at conditions of temperature pressure and contact time adjusted to condense the isoprene content of said C5 fraction with said ethylene, (6) continuously passing the Ca and C4 hydrocarbon fractions of step 3 through a separate reaction zone at conditions of temperature, pressure, and contact time adjusted to condense the propylene of the C3 fraction with the 1,3-butadiene of the C4 fraction, (7) recovering l-methyl-cyclohexene-i from the product of the reaction zone of step 5, and (8) recovering 4-methylcyclohexene-l from the product of thereaction zone of step 6 of the process.

5. The process as described in claim 4 Wherein the reaction zones of steps 5 and 6 are maintained at a temperature Within the range of from about 300 C. to about 375 C.

6. 'Ihe process as described in claim 4 wherein the contact time of isoprene with ethylene in step 5 and the contact time of 1,3-butadiene with propylene in step 6 are maintained within the range of from about 6 minutes to about 300 minutes.

propylene dimer at a temperature within the range of from about 750 C. to about 850" C. at

a, partial pressure of said dimer fraction less ALEX G. OBLAD. EVERETT GORIN.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,339,560 De Simo et al Jan. 18, 1944 2,349 232 Joshel May 16, 1944 2,404,056

Gorin et a1. July 16, 1946 

